Fabrication of S-scheme heterojunction between covalent organic frameworks and Ni-ZIF-8 and its photocatalytic hydrogen production performance

doi:10.1016/S1872-2067(25)64826-1

Abstract

Abstract:

Covalent organic frameworks (COFs) have garnered significant attention in photocatalysis owing to their exceptional light absorption capacities, tunable band structures, and high specific surface areas. However, the rapid recombination of photogenerated carriers in COFs remains a critical bottleneck limiting their practical application. In this study, a novel S-scheme heterojunction was constructed by integrating a Ni-doped zeolitic imidazolate framework-8 (Ni-ZIF-8) with Py-COF, effectively addressing this challenge. Through precisely controlled synthesis, the heterojunction achieves efficient and stable material combination, which not only significantly enhances photogenerated charge separation efficiency and markedly reduces recombination rates, but also demonstrates outstanding catalytic performance (162.77 mmol·h^-1·g^-1) and cycling stability in hydrogen evolution reaction. This study provides new insights into the design of efficient ZIF/COF-based heterojunction catalysts. This study provides an important theoretical foundation for the design of high-performance photocatalytic materials with broad application prospects.

Key words: Covalent organic frameworks, Ni-doped zeolitic imidazolate framework, S-scheme heterojunction, Photocatalytic, Hydrogen production

Xuan Zhang, Lin Zhou, Teng Yan, Xiaohu Zhang, Hao Chen. Fabrication of S-scheme heterojunction between covalent organic frameworks and Ni-ZIF-8 and its photocatalytic hydrogen production performance[J]. Chinese Journal of Catalysis, 2026, 80: 200-212.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(25)64826-1

https://www.cjcatal.com/EN/Y2026/V80/I1/200

Figures/Tables 13

Fig. 1. Synthesis of Py-COF.

Fig. 2. Synthesis of Ni-ZIF-8.

Fig. 3. Schematic diagram of Py-COF-[Ni(x%)-ZIF8]-y:z.

Fig. 4. (a) FT-IR spectra of Py-COF, TFPPY and BD. (c) 13C SS NMR of Py-COF (b), PXRD patterns and refined profiles of Py-COF. (d) XRD patterns of Ni-ZIF-8, Ni(15%)-ZIF8, Ni(30%)-ZIF8 and Ni(45%)-ZIF8. XRD patterns (e) and FT-IR spectra (f) of Py-COF, Ni(30%)-ZIF8 and Py-COF-[Ni(30%)-ZIF8]-10:1.

Fig. 5. (a) The SEM images of Py-COF. (b) The SEM images and TEM-mapping of Ni(30%)-ZIF8. (c) The SEM images of Py-COF-[Ni(30%)-ZIF8]-10:1. The TEM images of Py-COF (d), Ni(30%)-ZIF8 (e), and Py-COF-[Ni(30%)-ZIF8]-10:1 (f).

Fig. 6. The XPS survey spectrum (a), high-resolution XPS spectra of C 1s (b) and N 1s (c) for Py-COF, Ni(30%)-ZIF8 and Py-COF-[Ni(30%)-ZIF8]-10:1. (d) XPS spectra of Zn 2p for Ni(30%)-ZIF8 and Py-COF-[Ni(30%)-ZIF8]-10:1.

Fig. 7. (a) Comparison of photocatalytic H2 production activity of Py-COF, ZIF-8, Ni-ZIF-8, Ni(45%)-ZIF8, Py-COF-ZIF8]-10:1 and Py-COF-[Ni(45%)-ZIF8]-10:1. The effects of COF/Ni-ZIF-8 mass ratio (b) and Ni loading (c) on the performance of Py-COF-[Ni(30%)-ZIF8]-10:1. Influence of sacrificial reagent types (d), the influence of catalyst quality (e) and AA concentration (f) on the hydrogen production performance of Py-COF-[Ni(30%)-ZIF8]-10:1.

Fig. 8. (a) AQY test of Py-COF-[Ni(30%)-ZIF8]-10:1. (b) Comparison of properties of COFs-based heterojunctions in the literature.

Fig. 9. Cyclic stability tests (a), FT-IR (b), XRD (c) and UV-vis DRS (d) before and after reaction of Py-COF-[Ni(30%)-ZIF8]-10:1.

Fig. 10. UV-vis DRS spectra of Ni(30%)-ZIF8 (a) and, Py-COF and Py-COF-[Ni(30%)-ZIF8]-10:1 (b). (c) Tauc images of Py-COF. M-S images of Ni(30%)-ZIF8 (d) and Py-COF (e). (f) The suitable bandgap between the Py-COF and Ni(30%)-ZIF8 rendered it possible to build up S-schemed heterojunction.

Fig. 11. Transient photocurrent test (a) and EIS Nyquist plots (b) of Ni(30%)-ZIF8, Py-COF, Py-COF-[Ni(30%)-ZIF8]-10:1. (c) PL spectra of Py-COF and hybrid samples comprising Py-COF combined with [Ni(15%)-ZIF-8], [Ni(30%)-ZIF-8], and [Ni(45%)-ZIF-8] at varying ratios.

Fig. 12. In-situ XPS spectra of N 1s (a) and Zn 2p (b) over Py-COF-[Ni(30%)-ZIF8]-10:1.

Fig. 13. Schematic diagram of the photocatalytic hydrogen production mechanism of Py-COF-[Ni(30%)-ZIF8]-10:1.

References

[1]	F. Xie, C. Yuan, H. Tan, A. Z. Moshfegh, B. Zhu, J. Yu, Acta Phys.-Chim. Sin., 2024, 40, 2407013.
[2]	J. C. Xiang, J. J. Li, X. Yang, S. Y. Gao, R. Cao, Acta Phys.-Chim. Sin., 2023, 39, 2205039.
[3]	J. Zhu, S. Wageh, A. A. Al-Ghamdi, Chin. J. Catal., 2023, 49, 5-7.
[4]	Y. Zheng, H. Zhang, J. Xiong, Z. Zhao, D. Zhang, L. Chen, Fuel, 2024, 360, 130651.
[5]	Y. Fang, Y. Liu, H. Huang, J. Sun, J. Hong, F. Zhang, X. Wei, W. Gao, M. Shao, Y. Guo, Q. Tang, Y. Liu, Nat. Commun., 2024, 15, 4856.
[6]	K. Prakash, R. Deka, S. M. Mobin, Inorg. Chem. Front., 2024, 11, 6711-6752.
[7]	L. Que, C. Yuan, H. Zhang, M. Zhang, H. Zhai, X. Jian, Z. Zhou, J. Mater. Sci. Technol., 2025, 238, 13-23.
[8]	J. Zhang, G. Yang, B. He, B. Cheng, Y. Li, G. Liang, L. Wang, Chin. J. Catal., 2022, 43, 2530-2538.
[9]	S. Wei, R. Hou, Q. Zhu, I. Shakir, Z. Fang, X. Duan, Y. Xu, InfoMat, 2025, 7, e12646.
[10]	H. Guo, Z. Shu, D. Chen, Y. Tan, J. Zhou, F. Meng, T. Li, Chem. Phys., 2020, 533, 110714.
[11]	C. Chen, J. Zhang, H. Chu, L. Sun, G. Dawson, K. Dai, Chin. J. Catal., 2024, 63, 81-108.
[12]	Z. Fan, H. Lu, Y. Liu, C. Chang, X. Guo, G. Long, Z. Jin, Chem. Eng. J., 2023, 477, 147008.
[13]	L. Sun, L. Li, J. Yang, J. Fan, Q. Xu, Chin. J. Catal., 2022, 43, 350-358.
[14]	Y. Quan, J. Li, X. Li, R. Chen, Y. Zhang, J. Huang, J. Hu, Y. Lai, Appl. Catal. B Environ. Energy., 2025, 362, 124711.
[15]	X. An, J. Bian, K. Zhu, R. Liu, H. Liu, J. Qu, Chem. Eng. J., 2022, 442, 135279.
[16]	C. Yang, S. Wan, B. Zhu, J. Yu, S. Cao, Angew. Chem. Int. Ed., 2022, 61, e202208438.
[17]	H. Long, D. Gao, P. Wang, X. Wang, F. Chen, H. Yu, Appl. Catal. B, 2024, 340, 123270.
[18]	C.-H. Hsueh, C. He, J. Zhang, X. Tan, H. Zhu, W. M. Cheong, A.-Z. Li, X. Chen, H. Duan, Y. Zhao, C. Chen, J. Am. Chem. Soc., 2024, 146, 33857-33864.
[19]	W. Zhong, A. Meng, Y. Su, H. Yu, P. Han, J. Yu, Angew. Chem. Int. Ed., 2025, 64, e202425038.
[20]	Y. Wu, Y. Yang, M. Gu, C. Bie, H. Tan, B. Cheng, J. Xu, Chin. J. Catal., 2023, 53, 123-133.
[21]	M. Gu, Y. Yang, B. Cheng, L. Zhang, P. Xiao, T. Chen, Chin. J. Catal., 2024, 59, 185-194.
[22]	J. Fu, Q. Xu, J. Low, C. Jiang, J. Yu, Appl. Catal. B, 2019, 243, 556-565.
[23]	L. Zhang, J. Zhang, J. Yu, H. García, Nat. Rev. Chem., 2025, 9, 328-342.
[24]	P. Dong, A. Zhang, T. Cheng, J. Pan, J. Song, L. Zhang, R. Guan, X. Xi, J. Zhang, Chin. J. Catal., 2022, 43, 2592-2605.
[25]	B. An, W. Liu, J. Dong, N. Li, Y. Gao, L. Ge, Chin. J. Catal., 2024, 65, 113-125.
[26]	C.-X. Chen, Y.-Y. Xiong, X. Zhong, P. C. Lan, Z.-W. Wei, H. Pan, P.-Y. Su, Y. Song, Y.-F. Chen, A. Nafady, Sirajuddin, S. Ma, Angew. Chem. Int. Ed., 2022, 61, e202114071.
[27]	M. T. Thanh, T. V. Thien, P. D. Du, N. P. Hung, D. Q. Khieu, J. Porous Mater., 2018, 25, 857-869.
[28]	T. Huang, W. Zhang, S. Yang, L. Wang, G. Yu, SmartMat, 2024, 5, e1309.
[29]	Y. Li, L. Guo, Y. Lv, Z. Zhao, Y. Ma, W. Chen, G. Xing, D. Jiang, L. Chen, Angew. Chem. Int. Ed., 2021, 60, 5363-5369.
[30]	D. Zhu, L. B. Alemany, W. Guo, R. Verduzco, Polym. Chem., 2020, 11, 4464-4468.
[31]	J. Sun, H. Sekhar Jena, C. Krishnaraj, K. Singh Rawat, S. Abednatanzi, J. Chakraborty, A. Laemont, W. Liu, H. Chen, Y.-Y. Liu, K. Leus, H. Vrielinck, V. Van Speybroeck, P. Van Der Voort, Angew. Chem. Int. Ed., 2023, 62, e202216719.
[32]	F. P. Kinik, A. Ortega-Guerrero, D. Ongari, C. P. Ireland, B. Smit, Chem. Soc. Rev., 2021, 50, 3143-3177.
[33]	A. Garci, J. A. Weber, R. M. Young, M. Kazem-Rostami, M. Ovalle, Y. Beldjoudi, A. Atilgan, Y. J. Bae, W. Liu, L. O. Jones, C. L. Stern, G. C. Schatz, O. K. Farha, M. R. Wasielewski, J. Fraser Stoddart, Nat. Catal., 2022, 5, 524-533.
[34]	J. Shang, Y. Cui, P. Wu, P. Yu, K. Fu, L. Du, Z. Sun, Y. Liu, D. L. Phillips, Y. Zhou, Sens. Actuat. B, 2024, 402, 135053.
[35]	C. Chen, M. R. Alalouni, X. Dong, Z. Cao, Q. Cheng, L. Zheng, L. Meng, C. Guan, L. Liu, E. Abou-Hamad, J. Wang, Z. Shi, K.-W. Huang, L. Cavallo, Y. Han, J. Am. Chem. Soc., 2021, 143, 7144-7153.
[36]	Y.-S. Liu, R. Xue, K. Zhu, B. Yan, Angew. Chem. Int. Ed., 2025, 64, e202425436.
[37]	D. Chen, D. Luo, Y. He, J. Tian, Y. Yu, H. Wang, J. L. Sessler, X. Chi, J. Am. Chem. Soc., 2022, 144, 16755-16760.
[38]	Z. Lu, C. Yang, L. He, J. Hong, C. Huang, T. Wu, X. Wang, Z. Wu, X. Liu, Z. Miao, B. Zeng, Y. Xu, C. Yuan, L. Dai, J. Am. Chem. Soc., 2022, 144, 9624-9633.
[39]	A. Jati, S. Dam, S. Kumar, K. Kumar, B. Maji, Chem. Sci., 2023, 14, 8624-8634.
[40]	S. Ma, T. Deng, Z. Li, Z. Zhang, J. Jia, Q. Li, G. Wu, H. Xia, S.-W. Yang, X. Liu, Angew. Chem. Int. Ed., 2022, 61, e202208919.
[41]	Y. Tang, C. Liu, H. Zhu, X. Xie, J. Gao, C. Deng, M. Han, S. Liang, J. Zhou, Energy Storage Mater., 2020, 27, 109-116.
[42]	G. Kim, Y. Yea, L. K. Njaramba, Y. Yoon, S. Kim, C. M. Park, Environ. Res., 2022, 212, 113419.
[43]	S. Zuo, Y. Ding, H. Cheng, Z. Guan, X. Li, D. Li, Chem. Eng. J., 2024, 491, 152170.
[44]	L. Zhou, Y. Yi, Z. Fang, Chemosphere, 2022, 306, 135456.
[45]	Y. Yea, B. Cha, L. K. Njaramba, S. Kim, J. U. Choi, Y. Yoon, C. M. Park, Chem. Eng. J., 2024, 495, 153106.
[46]	Y.-N. Zhang, Z. Pei, Z.-H. Wang, C.-E. Wang, F.-F. Liang, L.-Q. Wei, Rare Met., 2024, 43, 2708-2718.
[47]	X. Yang, G. Wan, S. Ma, H. Xia, J. Wang, J. Liu, Y. Liu, G. Chen, Q. Bai, Talanta, 2020, 207, 120310.
[48]	Y. Wang, Q. Yang, F. Yi, R. Lu, Y. Chen, C. Liu, X. Li, C. Wang, H. Yan, ACS Appl. Mater. Interfaces, 2021, 13, 29916-29925.
[49]	H. Yan, Y. Liu, Y. Yang, H. Zhang, X. Liu, J. Wei, L. Bai, Y. Wang, F. Zhang, Chem. Eng. J., 2022, 431, 133404.
[50]	L. Yang, Y. Wang, J. Yuan, G. Wang, Q. Cao, H. Fei, M. Li, J. Shao, H. Li, J. Lu, Chem. Eng. J., 2022, 446, 137095.
[51]	Y.-P. Zhang, W. Han, Y. Yang, H.-Y. Zhang, Y. Wang, L. Wang, X.-J. Sun, F.-M. Zhang, Chem. Eng. J., 2022, 446, 137213.
[52]	Y. Liu, H. Tan, Y. Wei, M. Liu, J. Hong, W. Gao, S. Zhao, S. Zhang, S. Guo, ACS Nano, 2023, 17, 5994-6001.
[53]	F. Ahmadijokani, A. Ghaffarkhah, H. Molavi, S. Dutta, Y. Lu, S. Wuttke, M. Kamkar, O. J. Rojas, M. Arjmand, Adv. Funct. Mater., 2024, 34, 2305527.
[54]	H. Hu, X. Zhang, K. Zhang, Y. Ma, H. Wang, H. Li, H. Huang, X. Sun, T. Ma, Adv. Energy Mater., 2024, 14, 2303638.
[55]	X.-A. Li, Z.-Z. Liang, Y.-C. Zhou, J.-F. Huang, X.-L. Wang, L.-M. Xiao, J.-M. Liu, Aggregate, 2024, 5, e442.
[56]	Y. J. Zhou, P. Y. Dong, J. H. Liu, B. B. Zhang, B. Y. Zhang, X. G. Xi, J L. Zhang, Adv. Funct. Mater., 2025, 35, 2500733.
[57]	T.-X. Luan, L.-B. Xing, N. Lu, X.-L. Li, S. Kong, W. W. Yu, P.-Z. Li, Y. Zhao, J. Am. Chem. Soc., 2025, 147, 12704-12714.
[58]	D. Wu, F. He, Y. Dai, Y. Xie, Y. Ling, L. Liu, J. Zhao, H. Ye, Y. Hou, Chem. Eng. J., 2022, 446, 137003.
[59]	M. Sabir, M. Sayed, Z. Zeng, B. Cheng, W. Wang, C. Wang, J. Xu, S. Cao, Appl. Surf. Sci., 2025, 693, 162752.
[60]	S. F. Lee, E. Jimenez-Relinque, I. Martinez, M. Castellote, Catalysts, 2023, 13, 1000.